J. Chil. Chem. Soc.

, 53, Nº 2 (2008)

INTERFACE BETWEEN TWO IMMISCIBLE LIQUID ELECTROLYTES: A REVIEW

PETR VANÝSEK*1 AND LUIS BASÁEZ RAMÍREZ2

1
Northern Illinois University, Department of Chemistry and Biochemistry, DeKalb, IL 60115, USA.
2
Departamento de Química Analítica e Inorgánica, Facultad de Ciencias Químicas, Universidad de Concepción, Chile.
(Received: 13 December 2007 - Accepted: 22 April 2008)

ABSTRACT

An overview on electrochemistry on the interfaces between two immiscible electrolyte solutions is given.

Keywords: Review, ITIES, liquid-liquid interface, ion transfer, electron transfer, phase transfer catalysis, analytical applications, interfacial structure,
DIGISIM, modeling, X-ray reflectivity, double layer, immiscible liquids, electrochemistry.

BACKGROUND
The concept of immiscibility of certain liquids, such as oil and water, must
have been known to the humankind for millennia, and it must have captivated
early scientists just as much as it fascinates by its specific properties scientists
today. In our review we will focus on a specialized interface between two
immiscible liquids, an interface arising between two immiscible electrolyte
solutions. An electrolyte, a medium with ionic conductivity and mobile
charge carriers, introduces to the system of two immiscible phases additional
property not observed on an oil-water interface. Since the two phases are now
conductive and charge between the two phases can achieve equilibrium through
ion transport at the interface, the ionic conductivity of both the phases imparts
electrical potential difference on such interface.
This interface, the interface between two immiscible electrolytes (ITIES),
has some functional similarities with other types of interfaces. An interface is
defined as a boundary between two distinct phases. Hence, there is an interface
between a liquid and the glass wall of the container holding the liquid; there is
an interface between metal and liquid (for example copper metal and aqueous
solution of copper sulfate); there is an interface between water and some
organic solvents (for example nitrobenzene or 1,2-dichloroethane).
In order to observe ion transport across the interface due to applied
potential, it is first necessary to be able to apply appropriate potential on the
interface, i.e., the interface has to be made a polarizable interface. In order
to make a polarizable interface, it is first necessary to make the two phases
conductive to be able to apply potential from external electrodes. This is done
by dissolving suitable supporting electrolyte salts in each phase. To make the
interface polarizable, at least in a certain potential window, the salts dissolved
in the respective phase must be preferentially soluble in one phase, but not
in the other. The two salts often used are hydrophilic LiCl, which is used as
the supporting electrolyte for the aqueous phase and tetrabutylammonium
tetraphenylborate (TBATPB), which is lipohilic and is used as the supporting
electrolyte for the organic phase. Nitrobenzene or 1,2-dicholoroethane (DCE)
are used very often as the organic phase. Fig. 1 shows the potential window in
which such interface is polarizable.

From the electrochemical thermodynamic point of view the copper

metal/copper sulfate solution interface is treated in a fairly simple textbook
manner. The interface is described as a half cell and its potential is given by
the Nernst equation, utilizing the activity of the copper ions in the solution and
the standard reduction potential of Cu2+. When the potential of this interface
is studied in more detail it becomes obvious that the interfacial potential is
actually maintained by equilibrium between Cu2+ ions in the aqueous solution
and the activity, albeit abstract, of the copper ions in the metal. The general
reversible equilibrium

Cu2+ + 2 e Cu (1)

is the prerequisite for maintaining a steady and defined potential. In fact,

similar equilibria, e.g., between the activity of H3O+ in solution and activity of
OH- groups on surface of hydrated glass of a glass electrode is the principle of
the pH electrode. In short, any system that has an interface on which equilibrium
of charged species is dynamically established, will be a site of an interfacial
potential. By following this idea, it can be similarly envisioned that an interface
between two immiscible solutions, of which each contains certain activity of a
particular ion (K+, for example) will be a site of a potential difference driven by
the relative activities of potassium ion in each of the two phases. An example
of this is, in fact, an ion selective electrode based on a liquid membrane in
which the analyte is an aqueous solution containing dissolved potassium ions;
the sensing side is an organic solvent. An organic solvent will not typically
dissolve potassium ions. However, making them more lipophillic, for example,
by complexation with valinomycin, can make them soluble. This is known as
facilitated transport.
With proper setup, the interface between the two liquids can be made into
a boundary that responds, for electroanalytical purposes, like an electrode.
However, the distinction is that instead of reduction or oxidation of a species
on the electrode surface, a transport of a charged species thought the interface,
governs the observed current flow.
Figure 1. Curve of ITIES for a supporting electrolyte
The figure is a cyclic voltammogram, which shows the current flowing
through the interface in response to the applied potential. Within the potential
window, only little current flows, due mostly to charging of the interface
(charging current). Outside the window the ions of the supporting electrode
begin to transport into the opposite phase, contributing to the increasing
background current. Since it is traditional to assign the polarity of the interface
to the aqueous phase (as if the nonaqueous phase were grounded), the right
hand side of the curve in Fig. 1 corresponds to the aqueous phase becoming
increasing more positive. As the polarization continues (1 on the curve), TPB-
begins to transport from nitrobenzene to water and Li+ begins to be transported
form water to nitrobenzene. The relative contribution of the lipophilic anion
and the hydrophilic cation depend on the ranking of these ions on the scale
of the Gibbs energies of transfer1; since they are similar, both ions contribute

e-mail: pvanysek@niu.edu 1455

J. Chil. Chem. Soc., 53, Nº 2 (2008)

to the observed background current. After switching the direction of the scan
(2 on the curve), tetraphenylborate (TPB-) previously transported into water
crosses again back into nitrobenzene and Li+ from nitrobenzene crosses back
to water. As the cycle continues through the window of polarizability, the
current is mostly due to the charging of the interface; eventually, the aqueous
phase is becoming less and less positive with respect to the organic phase (3
on the curve) and transport of Cl- from water to nitrobenzene and transport of
tetrabutylammonium (TBA+) from nitrobenzene to water is observed. Finally,
after the potential switch (4 on the curve) the previously transported ions
return to their phase of origin, Cl- crosses back to water and TBA+ crosses to
nitrobenzene.
The potential at which the ion transfer across the interface happens is
related to the Gibbs energy of transfer. Thermodynamically, this energy and
the corresponding potential are normalized to the standard Gibbs energy of
transfer. It is a function of the particular ion, as well as a function of the solvent
pair studied. These values are available in various tables including a good web
based data base2 and Table I gives an example of some values for individual
ions transferring from water to nitrobenzene.
described in a skeletal form by Fermin et al7. The process involves metathesis
of stoichiometric amounts BTPPACl and LiTPFB dissolved in 2:1 mixture
of methanol and water, followed by recrystallization from hot acetone. The
initial precipitation requires additional amounts of the methanol-water mixture,
therefore it is not necessary to dissolve the starting material in least amount
of solvent. The solubility of the product is much higher in hot acetone than in
cold, so recrystallization is pretty simple. The melting point of our product was
223-225 oC. It should be noted that the acetone precipitate should be washed by
copious amounts of 2:1 mixture of methanol and water, to rinse out any starting
material, which otherwise causes large background current.
In the presence of an ion that can partition between the two phases it is
possible to obtain a voltammogram similar to that of a redox couple. Fig. 3
shows such case in which a cation with potential of transfer equal to 159 mV,
corresponding to the cesium ion, is being transferred across the interface.

Table I.- Standard potentials of transfer Δα β φo for selected individual

ions from water (phase α) to nitrobenzene (phase β)

Ion Δα β φo (mV)
Li+ 395
UO22+ 373
Mg2+ 361
Na+ 354
Fe3+ 319
K+ 242
Rb+ 201
Cs+ 159
Choline+ 117
Acetylcholine+ 49
TMeA+ 35
TBA+ - 248
TPB- 372
Picrate- 47
Dodecylsulfate- - 43
ClO4- - 83
Cl- - 324 Figure 3. Transfer of a Cs+ ion - DIGISIM simulated result.

The values for individual ions cannot be fundamentally determined
separately, one ion is always related to another in a chain of measurements.
Therefore, an assumption has been made that in the process of determining the
values for the cation and the ion of tetraphenylarsonium tetraphenylborate both
will have equal values, based on their similar sizes 3-6.
It is desirable to have the operating window as wide as possible. Although
TBATPB is traditionally used, more lipophilic salt has recently seen increase
in use (Fig. 2), the very lipophilic
It should be noted that the diffusion controlled process is described by the
same equations as a redox process – transfer across the interface is considered
fast compared to the diffusion control in both phases towards and away from
the interface, therefore the same math applies. However, the interface does not
experience a redox process. The difference between the diffusion controlled
redox and ITIES situation are compared in Fig. 4.

Figure 2. Bis(triphenylphosporanylidene)ammonium tetrakis (pentafluo-

rophenyl)borate

bis (triphenylphosporanylidene) ammonium tetrakis (pentafluorophenyl) borate

(BTPPATPFB). This salt has desirable wider potential window than TBATPB.
Its disadvantage is that it is rather expensive and so far it has to be prepared
rather than purchased. The preparation is not particularly involved and is Figure 4. Comparison between ITIES and a redox system

1456

In case A when negative potential is applied at the working electrode,
electron transfer takes place at the solution/metal electrode interface, iron(III)
is reduced to iron(II) and an electron moves “upwards” from the electrode to the
now-reduced iron ion. As a consequence, negative charge (arrow) flows through
the outside electrical circuit. In case B, when negative potential is applied at the
bottom (nonaqueous) phase in which ion A- is present, the negatively charged
ion moves “upwards” from the nonaqueous phase to the aqueous phase. As
a consequence, negative charge (arrow) flows through the outside electrical
circuit. Although the interfacial process in case A and B are different, the same
effect, current flow in the external electrical circuit, is observed.
The potential on the interface, as governed by a single ion that can
partition between the two phases in described by equation
(2)
which is similar in its appearance to the Nernst equation and in fact, it can be
derived by using the Nernst formalism. It is useful in situations where the other
ions, including the counterions, are well confined in their respective original
phases. However, when more that one ion participates in the equilibrium, the
equation becomes rather complicated8:
(3)
where Vα and Vβ are the volumes of the phases α and β (usually water, oil),
Δφ is the interfacial potential, Δφoi is the standard potential of transfer for the
individual ion (for example listed in Table I), m is the number of moles of each
of the ions, n is the charge (signed) of the respective ion, and γ is the activity of
the ion in the respective phase, α or β. For more than two species this equation
cannot be solved explicitly. However, with the help of an iterative solver it can
be successfully solved and used to calculate the interfacial potential from the
known values of the standard potentials, or, it can be used also to solve for a
particular unknown standard potential, if the partition coefficients are known9.
When the immiscible phases are in contact for sufficient length of time,
equilibrium according to the equation (3) will be established and there will
be no net current flow through the system. However, when such interface is
polarized from an external source, new equilibrium has to be established and
this can happen only trough reequilibration of the phases, by ion transport from
one phase to another and therefore, by current flow. In the most basic form the
expression describing the current at the interface is
(4)
where A is the interfacial area, F is the Faraday constant, k is the formal
rate constant of the transfer, α is the charge transfer coefficient, ci(w) and ci(o)
are the concentration of ion i in the aqueous and the oil phase respectively,
is the standard potential of transfer of ion i and is the potential difference
applied on the interface. This equation is in its formalism the same as the
Butler-Volmer equation written for redox processes. A more involved equation
can be written to include the Frumkin correction, which, as has been shown by
d’Epenoux et al10., applies also to ITIES. This more complex equation can be
found for example in the review publication11.
The interfaces between two immiscible electrolytes are of continuing interest
to many researchers, because of their relevance to such diverse applications such
as ion-pairing12,13, charge-transfer14,15, adsorption-desorption15, complexation16,
extraction17 acid-base processes18, catalysis19, micellar chemistry20, modeling
of interactions at biological cell membranes21-24, solvation dynamics25 and
fundamental studies of the nature of such interface26.
Ion distributions in electrolyte solutions near charged interfaces underlie
processes as diverse as electron and ion transfer at biomembranes and redox
processes at mineral-solution interfaces, and also influence many practical
J. Chil. Chem. Soc., 53, Nº 2 (2008)
applications in analytical chemistry and electrochemistry27-30.
The current associated with the ion transport across the interface is
governed by the same mass transport limitations as are redox processes on
a metal electrode/solution interface, namely, in unstirred systems with
fast electron transport the current governing step is diffusion. As long
as the transport of the ion on ITIES is fast (which it usually is) then the
current associated with the ion transport is governed by the same diffusion
equations. Therefore, we used successfully the modeling software DIGISIM31
(Bioanalytical Systems) to generate voltammograms which well agree with the
voltammograms obtained from an experiment. It is important to realize that
the potential window in ITIES is much narrower than is the typical working
range of an ideally polarizable electrode. Therefore, the potential of transfer
of the supporting electrolytes has to be included in the CV properties as well.
To generate a curve of the supporting mechanism we chose four mechanisms;
reduction of a species by one electron, with the redox potential being equal
to the standard potential of transport for the supporting electrolytes, i.e., Cl-,
Li+, TBA+ and TPB-. In practice, it is sufficient to include only the cation and
anion which are the more restrictive, in this case TBA+ and TPB-. To visualize
transport of a semihydrophilic ion across an interface, additional mechanism
(again, a reduction) is added, with the redox potential Eo in the software set
to the standard potential of transfer for the semihydrophilic ion. Fig. 3 shows
such simulation. The potentials for the restrictive ions of the supporting
electrolytes were set to 0.372 V (TPB-) and -0.248 V (TBA+) [Compare to the
standard potentials in Table I.]. The concentration of these ions was 0.1 mol/
l, value typical for such experiments. The potential of the semihydrophobic
ion was 0.159 V, chosen for illustration to fall between the potentials of the
supporting electrolytes. This corresponds to the potential of transport of cesium
ion between water and nitrobenzene. Its concentration was 1.0 mmol/l. The
scan rate was 25 mV/s. The actual scan was between –0.143 and + 0.272 V.
Additional adjustable parameter is the diffusion coefficient of the ion. We used
the default value, 1x10-5 cm2/s, which is somewhat higher than would be the
actual value. However, since the diffusion coefficient enters into the equations
as a square root, the results are not very sensitive to the exact value and for
demonstration purpose of suitability of DIGISIM to simulate ITIES curves this
is adequate.
An example of the electrochemical cell used for the experiments with
ITIES is shown in Fig. 5. It has some degree of complexity, because the issue
of a 4-electrode potentiostat and the issue of a reference electrode have to be
addressed.
In typical electrode electrochemistry a 3-electrode potentiostat is used,
with the working, the counter and the reference electrode. In principle, two
electrodes are needed; the 3-electrode setup allows the reference electrode not
to pass any current and therefore avoid polarization, and the current is supplied
by the counter (or auxiliary) electrode. Such setup allows to compensate for
the resistance of the solution. In ITIES we have to content with two sources
of resistance, both the aqueous and the nonaqueous solutions, with the ITIES
(functional equivalent of the electrode) sandwiched between them. Therefore
a special potentiostat is used, which has input for 2 reference electrodes, rather
than for one. Additionally, two counter electrodes are used. A number of
commercial potentiostats allow this connection either directly or after some
modifications. Solartron 1286 or 1287 is an example of the instrument used in
our laboratory.
The cell is operated in such a way that the reference electrode inputs
from the instrument are connected to the cell reference electrodes, which then
extend as Luggin capillaries to the vicinity of the L/L interface, marked ITIES
in the diagram. The two counter electrodes are connected to platinum flag
electrodes separated from the working solutions by a glass frit that prevents any
electrochemical products formed on the counter electrodes from contamination
of the interface. It should be noted that although there is no redox process
occurring on the interface, as long as there is current flowing through the cell,
redox processes (usually oxidation or reduction of the solvents) is taking place
on the platinum surface of the counter electrodes.
The potential of the whole cell, which includes the interface, is monitored
by the pair of the reference electrodes. The aqueous reference electrode is
usually simple Ag/AgCl electrode, which works well, because in most cases
the solution contains chloride, which pins the Ag/AgCl potential to a defined
value. The reference electrode for the non-aqueous phase is more involved.
It is a system with two interfaces. The actual metallic connection is realized
1457
J. Chil. Chem. Soc., 53, Nº 2 (2008)
by an Ag/AgCl electrode, immersed in aqueous solution of chloride. This
chloride has a counterion which is the same as is the cation in the nonaqueous
phase. Therefore, if the nonaqueous solution contains TBATPB, then the
aqueous solution will contain TBACl. This solution is then in contact with the
nonaqueous solution forming a reference interface; the two solutions in contact
have a common cation (TBA+ in this case), which equilibrates between the two
phases and sets up the interfacial potential according to equation (2). Therefore,
the potential applied by the potentiostat and reported on the voltammograms
is not usually the “standard potential of transfer;” rather, it is a potential that is
the sum of the interfacial potential, the potential of the two reference electrodes
and the potential of the reference interface.
The interface should be positioned between the two Luggin capillaries.
Different means of achieving this are possible. We are using a screw driven
piston that allows fine change of volume in the lower part of the cell, facilitating
thus adjustment of the interface.
Figure 5.- Diagram of the four-electrode cell used for ITIES studies
Analytical applications
Sun and Vanýsek32 demonstrated that the interface could be used for
determination of lead (II) ion by its transport across the interface. Because
lead (II) itself is quite hydrophilic, the transport must be facilitated by a ligand
former, such as polyethylene glycol.
The class of compounds seeing recent interest, the dendrimers, were also
investigated on the liquid-liquid interfaces33. In particular, it was the non-
redox active species, poly(propylenimine) and poly(amidoamine), for which
transfer across (acidified water)/1,2-dichloroethane interface was a viable
electroanalytical technique, since redox voltammetry is not possible. ITIES
voltammetry allowed low micromolar detection of dendrimers. It was observed
that the electrochemistry depended on the dendrimer family, the generation
number, and the experimental pH.
ITIES can be also successfully used for liquid-liquid extraction17, 34, 35. Jain
et al36. demonstrated the use of calixarene compound to preconcentrate and
transport lanthanum(III) ion. Transfer of permanganate ion37 was investigated
across the water-nitrobenzene interface with reported potential transfer, Gibbs
energy of transfer, the transfer rate constant and the apparent α coefficient
(symmetry factor equivalent in the redox electrochemistry) of this reaction. The
1458
ion transfer in this case is quasireversible, because following the permanganate
transport into the organic phase a chemical reaction occurs. The kinetic
parameters were obtained by cyclic voltammetry and chronopotentiometric
techniques.
For many applications and even for theoretical calculations dealing with L/
L interface it is necessary to know the diffusion coefficients and the transferring
species and also the effective charges of the transferred species. Yuan et al38.
demonstrated how to do this by a chronoamperometric method. To this end
they employed a micropipette electrode. Since the micropipette has a large time
constant (due to high resistance and relative large capacitance of the thin glass
surrounding the pipette), only measurements at times more than 5 ms were
possible. The authors performed finite element simulation to show validity of
the experimental data. For protamine they determined diffusion coefficient
to be (1.2± 0.1) x10-6 cm2/s, with ionic charge +20±1, which is close to the
excess positive charge of the molecule. For the ETH129 calcium ionophore
they determined that each ETH molecule39 transfers +0.67 charge per each Ca2+
ion, and +1 charge per Mg2+ transfer, which corresponds to formation of 1:3
complex for calcium and 1:2 complex for magnesium, in agreement with other
measurements. They also40 introduced the ionophore dinonylnaphthalenesul
fonate to facilitate transport of protamine at the L/L (water/dichloroethane)
interface.
The facilitated transport is very useful in situation where the ion itself falls
outside the potential window of the supporting electrolytes, usually because
it is too hydrophilic. To make the ion more oil soluble, complexation with
large, usually neutral species, is performed. Besides the already mentioned
analytical applications32 many other determinations with facilitated transport
were reported, of which only selected few can be mentioned16, 41-49. Biological,
physiological and pharmaceutical applications
Antibiotics are one class of compounds that have enjoyed particular
attention of the analytical work on the L/L interfaces. The typical function
of an antibiotic involves facilitated transport of ions (even though, it is
actually the ions, that facilitate the transport of the antibiotics) across a
biological membrane. Therefore, antibiotics with appropriate modification
will be transported across the ITIES. One of the early work demonstrated
determination of monensin, useful in synthesis of this compound for cattle
feed50-54, or nigericin55,56. Valinomycin, which forms very selective complex
with potassium, was studied on such ITIES57-63 as were β-lactam antibiotics and
their derivatives64, the channel former alamecithin65. It is not without interest
that antibiotics can be also synthesized, using a two phase method, on a liquid-
liquid interface66,67
The interface is also a natural site where polar and in particular large
molecules can be absorbed. Phospoholipids68-71, phosphatidylcholine21, 72-
74
, acetylcholine75-77, cellular protein annexin 78, and proteins (bovine serum
albumin), were all studied.
Jänchenová et al23, 24, studied adsorption and ion pairing interactions of
phospholipids on the water-1,2-dichloroethane interface. In particular, they
were interested in dipalmitoyl phosphatidyl choline (DPPC) (L-α-lecithin),
which appears to have rather complex behavior.
The authors propose the following sequence of steps23 .
A A A
L (o)
L (abs)
+ H+(w) HL+(ads) HL+(o) + A-(o) 6 HLA(o) 6 HA(o) + L (o)
(5)
where L is the zwitterionic form of DPPC and HL+ is its protonated form.
A
The five steps indicate that the process depends both on the potential difference
on the interface as well as the pH value. In the absence of multivalent ions a
monolayer is formed. However, in the presence of cerium(IV) sulfate it was
found that the DPPC forms multilayers, as indicated by slow transport. In fact,
the multilayers strongly slow down, even prevent, the transport of larger ions
such as TMeA+, PF6-, or K+ complexed with a crown-ether. Studies of such
biologically important compounds as dopamine79 and promazine80 were also
described.
Amemia presented several analytical papers where the property of the
L/L interface was used to detect species of biological importance. In81 he
demonstrated how meparin, negatively charged polysaccharide, can be detected
on the 1,2-dichloroethane interface. The detection requires use of ionophores to
accomplish the transfer. One of the more successful ionophores was octadecyl
trimethylammonium ion (as bromide). Unlike nonionic ionophore, this cationic

ionophore function is potential-dependent. To further increase detection limit,
the authors used preconcentration stripping method and achieved detection limit
of 0.012 unit/ml, significantly less than is the therapeutic (anticoagulant) value
(> 0.2 unit/ml). In82 he used protamines as a model species to demonstrate, first
time ever, voltammetric observation of phase transfer of biological polyions at
water-nitrobenzene interfaces.
The smooth, unrestrained liquid/liquid interface is of great advantage in the
x-ray studies on ITIES and it is certainly of some advantage in electroanalytical
applications where the surface area is that of the geometrical area. However,
in applications where large surface area is needed, such as in phase transfer
catalysis or in the use for energy applications in possible solar cells 82-87, the
limited surface area is a problem. Girault et al88 demonstrated that increase
in surface are can be performed when a 3-dimensional ITIES experiment is
performed on vitreous carbon.
An interesting nanotechnology procedure using liquid-liquid interfaces
was demonstrated by Glaser et al89, where the hexane-water interface was used
to align forming particles in a manner that a particle sphere consisting from two
different materials, one on each side, is formed. These particles, called Janus
particles after the Greek god with a face both on front and back of his head,
were formed from simultaneous growth of Au and Fe3O4. At least theoretically
Kornyshev et al90 suggested a principle of operation of a molecular device
on ITIES that could transform the energy of light into repetitive mechanical
motion.
When Nernst91,92 postulated the thermodynamic basis for electrode
equilibrium potential, leading now to what is known as the Nernst equation,
he also carried out with Riesenfeld experiments on liquid/liquid interfaces93.
However, early work on liquid interfaces was mostly non-electrochemical,
focusing on extraction processes, salting-out in ion solvent extraction,
measurements of physical properties such as interfacial tension, and
physiological studies on model membranes94-102. Systematic electrochemical
treatment did not begin until the late 1970’s when Koryta et al103 demonstrated
that the liquid/liquid interface lends itself to the same formalism as a solution/
metal interface and that similar, if not identical, experimental methodology
could be used. This led soon to development of various electrochemical
techniques to study the liquid/liquid interface, including, among others, studies
of the solvent dropping interface103-108, and studies of cyclic voltammetry108,
impedance measurements109-112, drop pressure method113, galvanostatic pulse
method114, 115, stripping voltammetry114, voltfluorometry 116-119, and transport
across a microinterface120-125. Electron transfer and photoinduced electron
transfer have been also observed on ITIES or theoretically treated19, 84, 86, 87, 126-
133
, as well as electrochemical catalysis19, 126, 127, 134, 135, adsorption15, 72, 136-138 and
electrodeposition26,139-154.
Newer techniques have been more recently applied to ITIES, such as the
quartz crystal microbalance155, 156, and scanning electrochemical microscopy on
liquid/liquid interfaces 75, 157-161.
Although the field of liquid/liquid electrochemistry is still relatively new,
more scientists are finding its results or methodology relevant and important
to their own work27-29. Recent efforts have led to many practical applications
in analytical chemistry and electrochemistry 162, 163. Charge transport across
an interface between two immiscible ionically conductive media is very
important both in naturally occurring systems and in designed applications.
Examples include ion transport across biological membranes15, 164, 165, drug
delivery166, behavior of ion-selective electrodes with liquid membranes and
similar sensors167, extraction processes in oil recovery168 or nuclear waste
reclamation and recovery169, 170, phase transfer catalysis in organic synthesis171,
pharmacology172-174, and many applications in electroanalytical chemistry130, 163,
174-178
, applied or developmental. Fundamentally, the interface is equivalent to
one side of a membrane of an ion selective electrode and thus these studies
usually draw on the work of ITIES as well. Microinterfaces are another useful
analytical tool, one already used to build sensors179 or to be used in the scanning
pipette electrochemical microscopy180-182 or in other analytical detection
schemes 121, 183-186. Ionic liquids which recently gained popularity in chemistry
research also show promise for applications in the ITIES work187-193.
Studies of charge transport, mostly ion but also electron, across the liquid/
liquid interface are often interpreted in terms of molecular or ionic ordering
at the interface. Both computer simulations and analytic theories aiming to
understand these electrochemical studies predict or assume very often existence
J. Chil. Chem. Soc., 53, Nº 2 (2008)
of molecular ordering at the interface27, 28, 193. However, there are few techniques
that are capable to probe directly this interface on the molecular length scale.
Such techniques include surface second harmonic generation137, 194-203, total-
internal reflection spectroscopy204-207, ac-potential modulation spectroscopy84,
197
, vibrational sum-frequency spectroscopy208, and time-resolved quasi-elastic
light scattering209, as well as neutron reflectivity210-213. To answer fundamental
questions about the structure and transport across this interface on the molecular
length scale a method using X-ray surface scattering was developed214-219. This
X-ray method provides information on interfacial molecular ordering on the
sub-nanometer length scale that is complementary to that provided by the
electrochemical and optical techniques.
Fundamental Studies
Electron transfer. Most of the analytical applications deal with transport
of ions across the interface, either directly or in some facilitated form using
a ligand to adjust the Gibbs energy of transport appropriately to fit into the
potential window. In fact, in the introduction we have made a clear distinction
between metal electrode and solution and an interface between the electrolytes,
and we pointed out that there is no redox reaction taking place at the ITIES.
However, in addition to ion transport across the ITIES, is also possible to
observe processes involving electron transfer. Such processes typically require
one redox system in each of the two phases and then the electron transfer can
occur on the interface. The redox couples used were for example ferrocene-
ferricinium for the nonaqueous phase and ferri-ferrocyanide in the aqueous
phase220. Other work investigating transport of electrons on ITIES, using
microinterfaces and scanning electrochemical micropipette methods, were
reported127, 130,220-229.
Interfacial Structure of Pure Interfaces. There are essentially two
basic, but opposing views of the structure of the interfacial structure of the
liquid/liquid boundary. One model predicts a molecularly sharp interface only
disturbed by contribution from capillary wave fluctuations. The other model
assumes interface in which regions of molecules originating from both phases
exist. These two views result in two very different chemical environments
for molecules at the interface. Interfacial tension and electrical capacitance
measurements at the interface between two electrolyte solutions have provided
arguments both for and against the sharp interfacial region 128, 230-237.
Either view of the interfacial structure has also appeared in the theoretical
literature129, 132, 133. These studies include a density functional approach that
leads to a mixed interfacial region at the interface with a thickness of several
solvent diameters238 and lattice-gas calculations that incorporate a mixed
interfacial region whose thickness is proportional to the miscibility of the two
solvents237, 239. Computer simulations based on molecular dynamics predict that
the interface should be locally sharp, only roughened by capillary waves214-240-
247
that originate form thermal movement of all particles in the matter.
The sharpness of the interface is not only a matter of academic curiosity.
It has also important practical electrochemical consequences. For example,
Marcus calculated rate constants for electron transfer between two redox species
in opposite phases, using either the sharp or the diffuse interface model131, 132.
His two results differed by two orders of magnitude. However, at that time the
scarce experimental data available and their experimental uncertainty, failed to
provide definitive answers to the question of the interfacial structure129.
The cause of disagreement on the nature of the interfacial structure was in
part due to a lack of techniques that can directly probe the interface. Interfacial
tension and capacitance, which were both used, probe only macroscopic
properties of the interface. The interfacial width of a nearly pure interface,
DCE/water(0.05 M KOH), which was measured by neutron reflectivity, was
found to be less than or equal to 1000 pm210. A vibrational sum-frequency
spectroscopy was used to study the DCE/water interface and it measured a small
optical response from polarization normal to the interfacial plane. Although
this result was interpreted as evidence for a mixed interfacial region, this
technique does not directly measure the interfacial width208. Schlossman et al.
used X-ray reflectivity to measure the width of the 2-heptanone/water interface
to be 700±20 pm215, which agrees well with the value 730 pm predicted from
capillary wave theory. This theory describes a fluctuating, molecularly sharp
interface. Molecular dynamics simulations are also in quantitative agreement
with Schlossman et al. results244. Schlossman et al. also measured the width of
the nitrobenzene/water interface at four different temperatures 214, 216. It turns out
that the measured interfacial width is actually significantly smaller than the one
1459
J. Chil. Chem. Soc., 53, Nº 2 (2008)

calculated from the capillary wave theory. For example, at 25 °C the measured About the authors:
width is 450±10 pm and the prediction is 520 pm. To explain this discrepancy,
the computer simulations suggest the presence of both weak molecular layering Luis Basáez Ramírez is Assistant Professor at the Department of
(of nitrobenzene at the interface) as well as dipole ordering parallel to the Analytical and Inorganic Chemistry, University of Concepción, Casilla 160-C,
interface244. It was shown that either layering or a bending rigidity, which could Concepción, Chile. He received his Ph.D. in 1995 from the Catholic University
result from dipole ordering, could explain these measurements214. The spatial of Valparaiso. He is presently appointed at the University of Concepción, in
resolution of the measurements did not allow to distinguish between these 1996-2001 as an Instructor and since 2001 as an Assistant Professor.
two possibilities. However, these results unequivocally demonstrate that the
interface is molecularly sharp. Petr Vanýsek is a Professor at the Chemistry and Biochemistry Department
of Northern Illinois University. His interests are in the field of liquid interfaces
If the model of a mixed solvent region at the interface would apply, the as well as sensors, impedance studies in general and in particular impedance
width of the interfacial region would have a contribution both from thermal studies on components of fuel cell. He is particularly interested in interpreting
fluctuations (capillary waves) as well as from the thickness of the mixed the impedance data correctly, with emphasis on unearthing experimental
region. These effects would lead, however, to a substantially larger width than artifacts. He is the Secretary of the Electrochemical Society and the Regional
was measured. Therefore, the results214 are not consistent with the theory of a Representative (USA) of the International Society of Electrochemistry. He
mixed solvent region. A recent measurement on water/hexane interface using received his Ph.D. in Physical Chemistry from the Czechoslovak Academy of
neutron reflectivity248, 249 confirmed X-ray results done on the same interface250. Sciences in Prague.
Although the water/hexadecane interface cannot be used for liquid/liquid
electrochemistry, the agreement of the results from both methods (X-rays, REFERENCES
600±20 pm; neutrons, 600±10 pm) confirm soundness of the reflectivity
measurements methods. 1. B. Behr, J. Gutknecht, H. Schneider, J. Stroka, J. Electroanal. Chem. 86,
289, (1978).
The interface between two liquid can have unusual electrowetting 2. H. H. Girault, http://lepa.epfl.ch/cgi/DB/InterrDB.pl. (Page verified
properties251. In fact, unusual effect of interfacial motion related to this effect active 17 April 2008).
has been described by many before252-259. 3. M. H. Abraham, T. Hill, H. C. Ling, R. A. Schultz, R. A. C. Watt, J.
Chem. Soc., Faraday Trans. I. 80, 489, (1984).
Ion Distributions at Interfaces. The liquid-liquid interface has two 4. O. Popovych, Crit. Rev. Anal. Chem. 1, 73, (1970).
important advantages over other interfaces if one wants to study ion distribution 5. J. Rais, Collect. Czech. Chem. Commun. 36, 3253, (1971).
near a surface. First is that the fluid interface does not impose an external 6. A. J. Parker, Chem. Rev. 69, 1, (1969).
structure on the adjacent liquid, unlike what would be expected from atomic 7. D. J. Fermin, H. D. Duong, Z. Ding, P.-F. Brevet, H. H. Girault, Phys.
size patterns on a solid surface. Second, if a solid surface or even a Langmuir Chem. Chem. Phys. 1, 1461, (1999).
monolayer on the water surface were to be used, their own bound charges, 8. L. Q. Hung, J. Electroanal. Chem. 115, 159, (1980).
which are not known, would have to be separately determined. 9. P. Vanysek. Determination of Gibbs energies of transfer of extremely
lipophilic supporting electrolytes in liquidliquid electrochemistry. in The
Ion distributions near a charged, planar surface can be predicted to some 58th Annual Meeting of the International Society of Electrochemistry.
degree by Gouy-Chapman theory, which solves the Poisson-Boltzmann 2007. Banff: ISE.
equation with simplifying assumptions260, 261. One limitation of this theory is that 10. B. D’Epenoux, P. Seta, G. Amblard, C. Gavach, J. Electroanal. Chem.
it assumes point-like volume-less ions, which interact through their mean field 99, 77, (1979).
in a structureless, continuum solvent. Extensive development and modification 11. P. Vanysek, Electrochemistry on Liquid/Liquid Interfaces. Lecture Notes
of the theory has addressed the limitations of the Gouy-Chapman theory262 and in Chemistry, ed. G. Berthier. Vol. 39. Springer-Verlag. Berlin. 1985, 106
predicted that for monovalent ions the deviations are largely a result of the pp.
difference between the interfacial and the bulk liquid structure. However, only 12. A. K. Kontturi, L. Kontturi, J. A. Manzanares, S. Mafe, L. Murtomaeki,
few experimental probes are directly sensitive to the structure near the charged Ber. Bunsen-Ges. Phys. Chem. 99, 1131, (1995).
interface, and the limit of validity of Gouy-Chapman theory has not been 13. R. D. Webster, D. Beaglehole, Phys. Chem. Chem. Phys. 2, 5660,
properly tested. The X-ray structural measurements, which demonstrate the (2000).
failure of the Gouy-Chapman theory, are in agreement with predictions based 14. S. Senthilkumar, R. A. W. Dryfe, R. Saraswathi, Langmuir. 23, 3455,
upon a molecular dynamics simulation that includes the effects of interfacial (2007).
liquid structure217. 15. S. Amemiya, X. Yang, T. L. Wazenegger, J. Am. Chem. Soc. 125, 11832,
(2003).
Classical electrochemical measurements at the liquid/liquid interface have 16. M. H. M. Cacote, C. M. Pereira, L. Tomaszewski, H. H. Girault, F. Silva,
revealed inadequacies of the Gouy-Chapman theory as well139, 233, 234, 237, 263-268. Electrochim. Acta. 49, 263, (2004).
A so-called Stern layer of preferentially adsorbed solvent molecules or ions 17. B. L. Rivas, S. Villegas, B. Ruf, I. M. Peric, J. Chil. Chem. Soc. 52, 1164,
is often used to explain measurements at the electrode/solution interface269. (2007).
The modified Gouy-Chapman-Stern theory includes the adsorbed layer plus 18. V. Gobry, G. Bouchard, P.-A. Carrupt, B. Testa, H. H. Girault, Helv.
the diffuse ion distribution described by the original Gouy-Chapman theory. Chim. Acta. 83, 1465, (2000).
Preferential adsorption of ions can occur at the liquid-liquid interface, although 19. R. Lahtinen, H. Jensen, D. J. Fermin, Catalysis and photocatalysis
tension measurements show that this does not occur on the nitrobenzene with at polarized molecular interfaces. An electrochemical approach
TBATPB and water with TBABr231. to catalytic processes based on two-phase systems, self-organized
microheterogeneous structures, and unsupported nanoparticles, in
CONCLUSIONS Interfacial Catalysis, A. G. Volkov, Editor. CRC Press, Boca Raton,
2003, p. 611.
It was out intention to outline the principle of the ITIES in electrochemistry 20. C. Gamboa, R. Barraza, A. F. Olea, J. Chil. Chem. Soc. 49, 303, (2004).
and to highlight some more recent or pressing aspects of this field. For better 21. T. Kakiuchi, T. Kondo, M. Kotani, M. Senda, Langmuir. 8, 169, (1992).
in-depth understanding several larger reviews are available 10, 129, 138, 271-274. 22. Y. Yoshida, K. Maeda, O. Shirai, J. Electroanal. Chem. 578, 17, (2005).
23. H. Jaenchenova, A. Lhotsky, K. Stulik, V. Marecek, J. Electroanal.
ACKNOWLEDGEMENTS Chem. 601, 101, (2007).
24. H. Jaenchenova, K. Stulik, V. Marecek, J. Electroanal. Chem. 604, 109,
PV acknowledges support from NSF-CHE0315691. (2007).
Basáez agradece al proyecto DIUC N° 207.021.025-1.0 and DIUC N° 25. G. Moakes, J. Janata, Acc. Chem. Res. 40, 720, (2007).
208.021.025-1.0 26. A. Trojanek, J. Langmaier, Z. Samec, J. Electroanal. Chem. 599, 160,
(2007).
27. A. G. Volkov, D. W. Deamer, Liquid-Liquid Interfaces: Theory and
Methods. 1996, 421 pp.

1460
 J. Chil. Chem. Soc., 53, Nº 2 (2008)

28. A. G. Volkov, Editor, Liquid Interfaces in Chemical, Biological, and 75. R. Gulaboski, C. M. Pereira, M. N. D. S. Cordeiro, I. Bogeski, E.
Pharmaceutical Applications. [In: Surfactant Sci. Ser., 2001; 95]. 2001, Ferreira, D. Ribeiro, M. Chirea, A. F. Silva, J. Phys. Chem. B. 109,
853 pp. 12549, (2005).
29. H. Watarai, N. Teramae, T. Sawada, Editors, Interfacial Nanochemistry: 76. B. Yu, B. Huang, P. Li, Microchem. J. 52, 10, (1995).
Molecular Science and Engineering at Liquid-Liquid Interfaces. 2005, 77. V. Marecek, Z. Samec, Anal. Lett. 14, 1241, (1981).
321 pp. 78. E. Bitto, M. Li, A. M. Tikhonov, M. L. Schlossman, W. Cho, Biochemistry.
30. H. H. Girault, Analytical and physical electrochemistry. EPFL Press. 39, 13469, (2000).
Lausanne, Switzerland. 2004 pp. 79. A. Berduque, R. Zazpe, D. W. M. Arrigan, Anal. Chim. Acta. 611, 156,
31. A. W. Bott, S. W. Feldberg, M. Rudolph, Curr. Sep. 13, 108, (1995). (2008).
32. Z. Sun, P. Vanysek, Anal. Chim. Acta. 228, 241, (1990). 80. L. M. A. Monzon, L. M. Yudi, Electrochim. Acta. 53, 2217, (2008).
33. A. Berduque, M. D. Scanlon, C. J. Collins, D. W. M. Arrigan, Langmuir. 81. J. Guo, Y. Yuan, S. Amemiya, Anal. Chem. 77, 5711, (2005).
23, 7356, (2007). 82. S. Amemiya, X. Yang, T. L. Wazenegger, J. Am. Chem. Soc. 125, 11832,
34. A. Oliva, A. Molinari, C. Avila, M. F. Flores, J. Chil. Chem. Soc. 51, 865, (2003).
(2006). 83. D. J. Fermin, Z. Ding, H. D. Duong, P. F. Brevet, H. H. Girault, Chem.
35. C. G. Gomez, C. R. von Plessing, G. M. C. Godoy, R. H. Reinbach, R. R. Commun., 1125, (1998).
Godoy, J. Chil. Chem. Soc. 50, 479, (2005). 84. D. J. Fermin, Z. Ding, H. D. Duong, P.-F. Brevet, H. H. Girault, J. Phys.
36. V. K. Jain, S. G. Pillap, H. C. Mandal, J. Chil. Chem. Soc. 52, 1177, Chem. B. 102, 10334, (1998).
(2007). 85. D. J. Fermin, H. D. Duong, Z. Ding, P. F. Brevet, H. H. Girault,
37. H. Heli, M. Shamsipur, M. F. Mousavi, Pol. J. Chem. 80, 313, (2006). Electrochem. Commun. 1, 29, (1999).
38. Y. Yuan, L. Wang, S. Amemiya, Anal. Chem. 76, 5570, (2004). 86. D. J. Fermin, H. Dung Duong, Z. Ding, P. F. Brevet, H. H. Girault, Phys.
39. U. Schefer, D. Ammann, E. Pretsch, U. Oesch, W. Simon, Anal. Chem. Chem. Chem. Phys. 1, 1461, (1999).
58, 2282, (1986). 87. D. J. Fermin, H. D. Duong, Z. Ding, P.-F. Brevet, H. H. Girault, J. Am.
40. Y. Yuan, S. Amemiya, Anal. Chem. 76, 6877, (2004). Chem. Soc. 121, 10203, (1999).
41. Y. Shao, M. V. Mirkin, Anal. Chem. 70, 3155, (1998). 88. S. Tan, M. Hojeij, B. Su, G. Meriguet, N. Eugster, H. H. Girault, J.
42. R. Zazpe, C. Hibert, J. O’Brien, Y. H. Lanyon, D. W. M. Arrigan, Lab Electroanal. Chem. 604, 65, (2007).
Chip. 7, 1732, (2007). 89. N. Glaser, D. J. Adams, A. Boeker, G. Krausch, Langmuir. 22, 5227,
43. P. O’ Dwyer, V. J. Cunnane, J. Electroanal. Chem. 581, 16, (2005). (2006).
44. G. Pieruz, P. Grassia, R. A. W. Dryfe, Desalination. 167, 417, (2004). 90. A. A. Kornyshev, M. Kuimova, A. M. Kuznetsov, J. Ulstrup, M. Urbakh,
45. B. Kralj, R. A. W. Dryfe, J. Electroanal. Chem. 560, 127, (2003). J. Phys.: Condens. Matter. 19, 375111/1, (2007).
46. D. Zhan, Y. Xiao, Y. Yuan, Y. He, B. Wu, Y. Shao, J. Electroanal. Chem. 91. W. Nernst, Z. Phys. Chem. (Frankfurt). 2, 613, (1888).
553, 43, (2003). 92. W. Nernst, Z. Phys. Chem. (Frankfurt). 4, 129, (1889).
47. M. V. Manzanares, Rev. Soc. Quim. Mex. 47, 66, (2003). 93. W. Nernst, E. H. Riesenfeld, Ann. Phys. 8, 600, (1902).
48. Y. Yatziv, I. Turyan, D. Mandler, J. Am. Chem. Soc. 124, 5618, (2002). 94. P. Bothorel, C. Lussan, C. R. l’Academie. Sci. 266, 2492, (1968).
49. Y. Kitatsuji, Z. Yoshida, H. Kudo, S. Kihara, J. Electroanal. Chem. 520, 95. W. D. Harkins, E. C. Humphery, J. Am. Chem. Soc. 38, 228, (1916).
133, (2002). 96. G. C. H. Ehrensvard, D. F. Cheesman, Svensk Kem. Tid. 53, 126,
50. J. Koryta, W. Ruth, P. Vanysek, A. Hofmanova, Anal. Lett. 15, 1685, (1941).
(1982). 97. E. K. Fischer, W. D. Harkins, J. Phys. Chem. 36, 98, (1932).
51. G. Du, J. Koryta, W. Ruth, P. Vanysek, J. Electroanal. Chem. 159, 413, 98. T. R. Bolam, J. Crowe, J. Phys. Chem. 35, 1448, (1931).
(1983). 99. R. P. Bell, J. Phys. Chem. 32, 882, (1928).
52. V. Marecek, H. Janchenova, M. Brezina, M. Betti, Anal. Chim. Acta. 100. P. L. du Nouy, C. R. l’Academie. Sci. 180, 1579, (1925).
244, 15, (1991). 101. J. H. Mathews, A. J. Stamm, J. Am. Chem. Soc. 46, 1071, (1924).
53. Z. Pang, D. Guo, X. Teng, E. Wang, Chin. J. Pharm. Anal. 5, 209, 102. W. D. Harkins, E. C. Humphery, J. Am. Chem. Soc. 38, 236, (1916).
(1985). 103. J. Koryta, P. Vanysek, M. Brezina, J. Electroanal. Chem. 67, 263,
54. J. Koryta, G. Du, W. Ruth, P. Vanysek, Faraday Discuss., 209, (1984). (1976).
55. A. Sabela, J. Koryta, O. Valent, J. Electroanal. Chem. 204, 267, (1986). 104. J. Koryta, P. Vanysek, M. Brezina, J. Electroanal. Chem. 75, 211,
56. J. Koryta, Wiad. Chem. 44, 579, (1990). (1977).
57. P. Vanysek, W. Ruth, J. Koryta, J. Electroanal. Chem. 148, 117, (1983). 105. P. Vanysek, J. Electroanal. Chem. 121, 149, (1981).
58. I. Koryta, N. Kozlov Iu, A. Gofmanova, V. Khalil, P. Vanysek, Antibiotiki. 106. J. Koryta, M. Brezina, A. Hofmanova, D. Homolka, H. Le Quoc, W.
28, 810, (1983). Khalil, V. Marecek, Z. Samec, S. K. Sen, et al., Bioelectrochem.
59. H. Ohde, K. Maeda, O. Shirai, Y. Yoshida, S. Kihara, J. Electroanal. Bioenerget. 7, 61, (1980).
Chem. 438, 139, (1997). 107. P. Vanysek, M. Behrendt, J. Electroanal. Chem. 130, 287, (1981).
60. E. Makrlik, P. Vanura, J. Halova, Pol. J. Chem. 81, 1531, (2007). 108. D. Homolka, L. Q. Hung, A. Hofmanova, M. W. Khalil, J. Koryta, V.
61. E. Makrlik, P. Vanura, Acta Chim. Slov. 54, 375, (2007). Marecek, Z. Samec, S. K. Sen, P. Vanysek, J. Weber, Anal. Chem. 52,
62. E. Makrlik, P. Vanura, J. Radioanal. Nucl. Chem. 268, 641, (2006). 1606, (1980).
63. E. Makrlik, P. Vanura, J. Radioanal. Nucl. Chem. 268, 155, (2006). 109. Z. Samec, V. Marecek, D. Homolka, J. Electroanal. Chem. 126, 121,
64. L. Basaez, P. Vanysek, J. Pharm. Biomed. Anal. 19, 183, (1999). (1981).
65. D. P. Tieleman, H. J. C. Berendsen, M. S. P. Sansom, Biophys. J. 80, 331, 110. T. Wandlowski, S. Racinsky, V. Marecek, Z. Samec, J. Electroanal.
(2001). Chem. 227, 281, (1987).
66. A. Illanes, L. Wilson, O. Corrotea, L. Tavernini, F. Zamorano, C. Aguirre, 111. T. Wandlowski, V. Marecek, Z. Samec, J. Electroanal. Chem. 242, 277,
J. Mol. Catal. B Enzym. 47, 72, (2007). (1988).
67. C. Aguirre, P. Opazo, M. Venegas, R. Riveros, A. Illanes, Process 112. P. Vanysek, I. C. Hernandez, J. Xu, Microchem. J. 41, 327, (1990).
Biochem. (Amsterdam). 41, 1924, (2006). 113. J. D. Reid, O. R. Melroy, R. P. Buck, J. Electroanal. Chem. 147, 71,
68. T. Kondo, T. Kakiuchi, M. Senda, Biochim. Biophys. Acta. 1, (1992). (1983).
69. L. Murtomaki, J. A. Manzanares, S. Mafe, K. Kontturi, Surf. Sci. Ser. 95, 114. V. Marecek, Z. Samec, Anal. Chim. Acta. 151, 265, (1983).
533, (2001). 115. V. Marecek, Z. Samec, J. Electroanal. Chem. 149, 185, (1983).
70. Z. Samec, A. Trojanek, P. Krtil, Faraday Discuss. 129, 301, (2005). 116. T. Kakiuchi, Y. Takasu, Anal. Chem. 66, 1853, (1994).
71. J. Koryta, L. Q. Hung, A. Hofmanova, Stud. Biophys. 90, 25, (1982). 117. T. Kakiuchi, Y. Takasu, J. Electroanal. Chem. 365, 293, (1994).
72. Z. Samec, A. Trojanek, H. H. Girault, Electrochem. Commun. 5, 98, 118. T. Kakiuchi, Y. Takasu, J. Electroanal. Chem. 381, 5, (1995).
(2003). 119. H. Nagatani, S. Suzuki, D. J. Fermin, H. H. Girault, K. Nakatani, Anal.
73. H. H. J. Girault, D. J. Schiffrin, J. Electroanal. Chem. 179, 277, (1984). Bioanal. Chem. 386, 633, (2006).
74. T. Kakiuchi, M. Kotani, J. Noguchi, M. Nakanishi, M. Senda, J. Colloid 120. J. A. Campbell, H. H. Girault, J. Electroanal. Chem. 266, 465, (1989).
Interface Sci. 149, 279, (1992). 121. A. A. Stewart, G. Taylor, H. H. Girault, J. McAleer, J. Electroanal.
Chem. 296, 491, (1990).

1461
J. Chil. Chem. Soc., 53, Nº 2 (2008)
122. A. A. Stewart, Y. Shao, C. M. Pereira, H. H. Girault, J. Electroanal.
Chem. 305, 135, (1991).
123. Y. Shao, H. H. Girault, J. Electroanal. Chem. 334, 203, (1992).
124. T. Ohkouchi, T. Kakutani, T. Osakai, M. Senda, Anal. Sci. 7, 371,
(1991).
125. V. Sladkov, V. Guillou, S. Peulon, M. L’Her, J. Electroanal. Chem. 573,
129, (2004).
126. R. M. Lahtinen, D. J. Fermin, H. Jensen, K. Kontturi, H. H. Girault,
Electrochem. Commun. 2, 230, (2000).
127. D. J. Fermin, R. Lahtinen, Surf. Sci. Ser. 95, 179, (2001).
128. H. H. J. Girault, D. J. Schiffrin, J. Electroanal. Chem. 244, 15, (1988).
129. G. Geblewicz, D. J. Schiffrin, J. Electroanal. Chem. 244, 27, (1988).
130. M. L’Her, V. Sladkov, Electron transfer at the liquid-liquid interface, in
Trends in Molecular Electrochemistry, A. J. L. Pombeiro, C. Amatore,
Editors. CRC Press, Boca Raton, 2004, p. 503.
131. T. Solomon, A. J. Bard, J. Phys. Chem. 99, 17487, (1995).
132. R. A. Marcus, J. Phys. Chem. 94, 7742, (1990).
133. R. A. Marcus, J. Phys. Chem. 94, 4152, (1990).
134. Y. Shao, M. V. Mirkin, J. F. Rusling, J. Phys. Chem. B. 101, 3202,
(1997).
135. F. G. Chevallier, T. J. Davies, O. V. Klymenko, L. Jiang, T. G. J. Jones,
R. G. Compton, J. Electroanal. Chem. 580, 265, (2005).
136. B. Su, N. Eugster, H. H. Girault, J. Electroanal. Chem. 577, 187,
(2005).
137. J. Zhang, C. J. Slevin, L. Murtomaeki, K. Kontturi, D. E. Williams, P. R.
Unwin, Langmuir. 17, 821, (2001).
138. R. R. Naujok, D. A. Higgins, D. G. Hanken, R. M. Corn, J. Chem. Soc.,
Faraday Trans. 91, 1411, (1995).
139. H. H. Girault, Charge transfer across liquid-liquid interfaces, in Modern
Aspects of Electrochemistry, J. O. M. Bockris, B. E. Conway, R. E.
White, Editors. Plenum Publishing Corp., New York, 1993, p. 1.
140. M. Vignali, R. Edwards, V. J. Cunnane, J. Electroanal. Chem. 592, 37,
(2006).
141. C. Johans, R. Lahtinen, K. Kontturi, D. J. Schiffrin, J. Electroanal.
Chem. 488, 99, (2000).
142. M. Platt, R. A. W. Dryfe, J. Electroanal. Chem. 599, 323, (2007).
143. Y. Luan, M. An, G. Lu, Appl. Surf. Sci. 253, 459, (2006).
144. M. Vignali, R. A. H. Edwards, M. Serantoni, V. J. Cunnane, J. Electroanal.
Chem. 591, 59, (2006).
145. V. Mirceski, R. Gulaboski, J. Phys. Chem. B. 110, 2812, (2006).
146. V. Mirceski, Electrochem. Commun. 8, 123, (2006).
147. I. Turyan, M. Etienne, D. Mandler, W. Schuhmann, Electroanalysis. 17,
538, (2005).
148. M. Platt, R. A. W. Dryfe, Phys. Chem. Chem. Phys. 7, 1807, (2005).
149. E. Tada, Y. Oishi, H. Kaneko, Electrochem. Solid State Lett. 8, C26,
(2005).
150. M. Platt, R. A. W. Dryfe, E. P. L. Roberts, Electrochim. Acta. 49, 3937,
(2004).
151. C. R. C. Johans, Novel routes to metal nanoparticles: electrodeposition
and reactions at liquid/liquid interfaces, in Department of Chemical
Technology. 2003, Helsiki University of Technology: Espoo, Finland. p.
56 pp.
152. A. Eftekhari, Appl. Surf. Sci. 227, 331, (2004).
153. E. Tada, H. Kaneko, Chem. Lett., 1306, (2000).
154. M. Guainazzi, G. Silvestri, G. Serravalle, J. Chem. Soc., Chem. Commun.,
200, (1975).
155. P. Vanysek, L. A. Delia, Electroanalysis. 18, 371, (2006).
156. P. Vanysek, Proceedings of the IEEE International Frequency Control
Symposium. 51, 49, (1997).
157. T. Solomon, A. J. Bard, Anal. Chem. 67, 2787, (1995).
158. T. Solomon, A. J. Bard, Bull. Chem. Soc. Ethiopia. 11, 55, (1997).
159. C. Wei, A. J. Bard, M. V. Mirkin, J. Phys. Chem. 99, 16033, (1995).
160. M. Tsionsky, A. J. Bard, M. V. Mirkin, J. Phys. Chem. 100, 17881,
(1996).
161. Y. Selzer, D. Mandler, J. Electroanal. Chem. 409, 15, (1996).
162. P. Vanysek, Anal. Chem. 62, 827A, (1990).
163. F. Reymond, D. Fermin, H. J. Lee, H. H. Girault, Electrochim. Acta. 45,
2647, (2000).
164. R. B. Gennis, Biomembranes: Molecular Structure and Function.
Springer. New York. 1988, 533 pp.
165. T. Spataru, N. Spataru, N. Bonciocat, C. Luca, Bioelectrochemistry. 62,
67, (2004).
1462
166. A. Maelkiae, P. Liljeroth, A.-K. Kontturi, K. Kontturi, J. Phys. Chem. B.
105, 10884, (2001).
167. S. A. Dassie, A. M. Baruzzi, J. Electroanal. Chem. 492, 94, (2000).
168. M. J. Tupy, H. W. Blanch, C. J. Radke, Ind. Eng. Chem. Res. 37, 3159,
(1998).
169. G. W. Stevens, J. M. Perera, F. Grieser, Curr. Opin. Colloid Interface.
Sci. 2, 629, (1997).
170. J. Plesek, B. Gruner, S. Hermanek, J. Baca, V. Marecek, J. Janchenova,
A. Lhotsky, K. Holub, P. Selucky, J. Rais, I. Cisarova, J. Caslavsky,
Polyhedron. 21, 975, (2002).
171. C. Forssten, J. Strutwolf, D. E. Williams, Electrochem. Commun. 3, 619,
(2001).
172. R. Gulaboski, M. N. D. S. Cordeiro, N. Milhazes, J. Garrido, F. Borges,
M. Jorge, C. M. Pereira, I. Bogeski, A. H. Morales, B. Naumoski, A. F.
Silva, Anal. Biochem. 361, 236, (2007).
173. L. Basaez, I. Peric, C. Aguirre, P. Vanysek, Bol. Soc. Chil. Quim. 46, 203,
(2001).
174. H. Alemu, Pure Appl. Chem. 76, 697, (2004).
175. F. Reymond, H. J. Lee, J. S. Rossier, L. Tomaszewski, R. Ferrigno, C. M.
Pereira, H. H. Girault, Chimia. 53, 103, (1999).
176. J. Koryta, Selective Electr. Rev. 13, 133, (1991).
177. B. Liu, M. V. Mirkin, Electroanalysis. 12, 1433, (2000).
178. Z. Samec, E. Samcova, H. H. Girault, Talanta. 63, 21, (2004).
179. B. J. Seddon, Y. Shao, J. Fost, H. H. Girault, Electrochim. Acta. 39, 783,
(1994).
180. D. Zhan, X. Li, W. Zhan, F.-R. F. Fan, A. J. Bard, Anal. Chem. 79, 5225,
(2007).
181. D. A. Walsh, J. L. Fernandez, J. Mauzeroll, A. J. Bard, Anal. Chem. 77,
5182, (2005).
182. P. Sun, Z. Zhang, Z. Gao, Y. Shao, Angew. Chem. Int. Ed. 41, 3445,
(2002).
183. Q. Qian, G. S. Wilson, K. Bowman-James, Electroanalysis. 16, 1343,
(2004).
184. Q. Qian, G. S. Wilson, K. Bowman-James, H. H. Girault, Anal. Chem.
73, 497, (2001).
185. R. Zazpe, C. Hibert, J. O’Brien, Y. H. Lanyon, D. W. M. Arrigan, Lab
Chip. 7, 1732, (2007).
186. F. Quentel, C. Elleouet, V. Mirceski, V. Agmo Hernandez, M. L’Her, M.
Lovric, S. Komorsky-Lovric, F. Scholz, J. Electroanal. Chem. 611, 192,
(2007).
187. J. Langmaier, Z. Samec, Electrochem. Commun. 9, 2633, (2007).
188. R. Ishimatsu, N. Nishi, T. Kakiuchi, Langmuir. 23, 7608, (2007).
189. R. Ishimatsu, N. Nishi, T. Kakiuchi, Chem. Lett. 36, 1166, (2007).
190. T. Kakiuchi, Anal. Chem. 79, 6442, (2007).
191. V. A. Hernandez, F. Scholz, Electrochem. Commun. 8, 967, (2006).
192. K. Tanaka, N. Nishi, T. Kakiuchi, Anal. Sci. 20, 1553, (2004).
193. W. Schmickler, Interfacial Electrochemistry. Oxford University Press.
New York. 1996, 304 pp.
194. K. L. Kott, D. A. Higgins, R. J. McMahon, R. M. Corn, J. Am. Chem.
Soc. 115, 5342, (1993).
195. D. A. Higgins, R. M. Corn, J. Phys. Chem. 97, 489, (1993).
196. D. A. Higgins, R. R. Naujok, R. M. Corn, Chem. Phys. Lett. 213, 485,
(1993).
197. H. Nagatani, A. Piron, P.-F. Brevet, D. J. Fermin, H. H. Girault, Langmuir.
18, 6647, (2002).
198. J. G. Frey, Second harmonic generation at liquid/liquid interfaces, in
Interfacial Nanochemistry, H. Watari, N. Teramae, T. Sawada, Editors.
Springer, New York, 2005, p. 1.
199. J. C. Conboy, G. L. Richmond, Electrochim. Acta. 40, 2881, (1995).
200. J. C. Conboy, G. L. Richmond, J. Phys. Chem. B. 101, 983, (1997).
201. H. H. Girault, M. Hojeij, B. Su, Abstracts of Papers, 233rd ACS National
Meeting, Chicago, IL, United States, March 25-29, 2007. PHYS,
(2007).
202. J. C. Conboy, G. L. Richmond, Total internal reflection second harmonic
generation from the interface between two immiscible electrolyte
solutions. 1995, Dep. Chem., Oregon Univ., Eugene, OR, USA. p. 15
pp.
203. R. M. Corn, R. N. Naujok, H. J. Paul, Book of Abstracts, 210th ACS
National Meeting, Chicago, IL, August 20-24. COLL, (1995).
204. S. Ishizaka, N. Kitamura, Bull. Chem. Soc. Japan. 74, 1983, (2001).
205. M. J. Tupy, Protein adsorption dynamics at the oil/water interface as
studied by total internal reflection fluorescence spectroscopy. 1998,
University of California at Berkeley: Berkeley. p. 268 pp.
 J. Chil. Chem. Soc., 53, Nº 2 (2008)

206. J. M. Perera, G. W. Stevens, F. Grieser, Colloids Surf., A. 95, 185, 239. S. Frank, W. Schmickler, J. Electroanal. Chem. 483, 18, (2000).
(1995). 240. I. Benjamin, Science. 261, 1558, (1993).
207. J. C. Conboy, J. L. Daschbach, G. L. Richmond, J. Phys. Chem., 9688, 241. I. Benjamin, Chem. Rev. 96, 1449, (1996).
(1994). 242. L. Benjamin, J. Chem. Phys. 97, 1432, (1992).
208. D. S. Walker, M. G. Brown, C. L. McFearin, G. L. Richmond, J. Phys. 243. D. Michael, I. Benjamin, J. Electroanal. Chem. 450, 335, (1998).
Chem. B. 108, 2111, (2004). 244. P. A. Fernandes, M. N. D. S. Cordeiro, J. A. N. F. Gomes, J. Phys. Chem.
209. H. Yui, Y. Ikezoe, T. Sawada, Anal. Sci. 20, 1501, (2004). B. 103, 8930, (1999).
210. J. Strutwolf, A. L. Barker, M. Gonsalves, D. J. Caruana, P. R. Unwin, D. 245. M. R. Philpott, T.-T. Lin, J. N. Glosli. Molecular Dynamics Study of
E. Williams, J. R. P. Webster, J. Electroanal. Chem. 483, 163, (2000). Neutral and Charged Liquid-Liquid Interfaces. in Modeling of Processes
211. J. R. P. Webster, Abstracts of Papers, 234th ACS National Meeting, at Electrochemical Interfaces and in Electrochemical Systems. 1999.
Boston, MA, United States, August 19-23, 2007. PHYS, (2007). Seattle: The Electrochemical Society.
212. A. Zarbakhsh, A. Querol, J. Bowers, M. Yaseen, J. R. Lu, J. R. P. Webster, 246. P. Tarazona, R. Checa, E. Chacon, Phys. Rev. Lett. 99, 196101/1,
Langmuir. 21, 11704, (2005). (2007).
213. A. Zarbakhsh, A. Querol, J. Bowers, J. R. P. Webster, Faraday Discuss. 247. J. Chowdhary, B. M. Ladanyi, Abstracts of Papers, 232nd ACS National
129, 155, (2005). Meeting, San Francisco, CA, United States, Sept. 10-14, 2006. COLL,
214. G. Luo, S. Malkova, S. V. Pingali, D. G. Schultz, B. Lin, M. Meron, I. (2006).
Benjamin, P. Vanysek, M. L. Schlossman, J. Phys. Chem. B. 110, 4527, 248. D. M. Mitrinovic, A. M. Tikhonov, M. Li, Z. Huang, M. L. Schlossman,
(2006). Phys. Rev. Lett. 85, 582, (2000).
215. G. Luo, S. Malkova, S. V. Pingali, D. G. Schultz, B. Lin, M. Meron, 249. A. Zarbakhsh, J. Bowers, J. R. P. Webster, Langmuir. 21, 11596, (2005).
T. J. Graber, J. Gebhardt, P. Vanysek, M. L. Schlossman, Electrochem. 250. M. L. Schlossman, Curr. Opin. Colloid Interface. Sci. 7, 235, (2002).
Commun. 7, 627, (2005). 251. C. W. Monroe, M. Urbakh, A. A. Kornyshev, J. Phys.: Condens. Matter.
216. G. Luo, S. Malkova, S. V. Pingali, D. G. Schultz, B. Lin, M. Meron, T. 19, 375113/1, (2007).
J. Graber, J. Gebhardt, P. Vanysek, M. L. Schlossman, Faraday Discuss. 252. R. Chertcoff, A. Calvo, I. Paterson, M. Rosen, J. P. Hulin, J. Colloid
129, 23, (2005). Interface Sci. 154, 194, (1992).
217. G. Luo, S. Malkova, a. Yoon, D. G. Schultz, B. Lin, M. Meron, I. 253. P. Joos, R. V. Bogaert, J. Colloid Interface Sci. 56, 213, (1976).
Benjamin, P. Vanysek, M. L. Schlossman, Science. 311, 216, (2006). 254. M. Dupeyrat, J. Michel, Experientia Suppl. 18, 269, (1971).
218. G. Luo, S. Malkova, J. Yoon, D. Schultz, B. Lin, I. Benjamin, P. Vanysek, 255. M. Dupeyrat, E. Nakache, C. R. Acad. Sci. (Paris). 277, 599, (1973).
M. L. Schlossman, Abstracts of Papers, 233rd ACS National Meeting, 256. E. Nakache, M. Dupeyrat, M. Vignes-Adler, Faraday Discuss. Chem.
Chicago, IL, United States, March 25-29, 2007. PHYS, (2007). Soc. 77, 189, (1984).
219. G. Luo, S. Malkova, J. Yoon, D. G. Schultz, B. Lin, M. Meron, I. 257. P. Van Remoortere, P. Joos, J. Colloid Interface Sci. 160, 397, (1993).
Benjamin, P. Vanysek, M. L. Schlossman, J. Electroanal. Chem. 593, 258. A. A. Kornyshev, A. M. Kuznetsov, M. Urbakh, J. Chem. Phys. 117,
142, (2006). 6766, (2002).
220. T. Kakiuchi, T. Takaishi, Proceedings - Electrochemical Society. 97-19, 259. A. L. Barker, P. R. Unwin, J. Phys. Chem. B. 105, 12019, (2001).
538, (1997). 260. Gouy, C. R. l’Academie. Sci. 149, 654, (1910).
221. A. A. Stewart, J. A. Campbell, H. H. Girault, M. Eddowes, Ber. Bunsen- 261. D. L. Chapman, Phil. Mag. Ser. 6. 25, 475, (1913).
Ges. Phys. Chem. 94, 83, (1990). 262. S. Levine, C. W. Outhwaite, L. B. Bhuiyan, J. Electroanal. Chem. 123,
222. X. Lu, H. Zhang, L. Hu, C. Zhao, L. Zhang, X. Liu, Electrochem. 105, (1981).
Commun. 8, 1027, (2006). 263. C. M. Pereira, A. Martins, M. Rocha, C. J. Silva, F. Silva, J. Chem. Soc.,
223. X. Lu, L. Hu, X. Wang, Electroanalysis. 17, 953, (2005). Faraday Trans. 90, 143, (1994).
224. M. V. Mirkin, M. Tsionsky, Charge-transfer at the liquid/liquid interface, 264. Y. Cheng, V. J. Cunnane, D. J. Schiffrin, L. Murtomaki, K. Kontturi, J.
in Scanning Electrochemical Microscopy, A. J. Bard, M. V. Mirkin, Chem. Soc., Faraday Trans. 87, 1665, (1991).
Editors. CRC Press, Boca Raton, 2001, p. 299. 265. Y. Cheng, V. J. Cunnane, D. J. Schiffrin, L. Mutomaki, K. Kontturi, J.
225. J. Zhang, P. R. Unwin, Phys. Chem. Chem. Phys. 4, 3820, (2002). Chem. Soc., Faraday Trans. 87, 107, (1991).
226. A. L. Barker, P. R. Unwin, J. Zhang, Electrochem. Commun. 3, 372, 266. C. M. Pereira, W. Schmickler, F. Silva, M. J. Sousa, J. Electroanal.
(2001). Chem. 436, 9, (1997).
227. B. Quinn, K. Kontturi, J. Electroanal. Chem. 483, 124, (2000). 267. O. Pecina, J. P. Badiali, Phys. Rev. E. Sta. Phys. Plasma Fluid. Rel. 58,
228. J. Zhang, A. L. Barker, P. R. Unwin, J. Electroanal. Chem. 483, 95, 6041, (1998).
(2000). 268. H. H. Girault, D. J. Schiffrin, Electrochemistry of liquid-liquid interfaces,
229. A. L. Barker, P. R. Unwin, J. Phys. Chem. B. 104, 2330, (2000). in Electroanalytical Chemistry, A. J. Bard, Editor. Marcel Dekker, New
230. T. Kakiuchi, M. Senda, Bull. Chem. Soc. Japan. 56, 1322, (1983). York, 1989, p. 1.
231. C. Gavach, P. Seta, B. D’Epenoux, J. Electroanal. Chem. 83, 225, 269. O. Stern, Z. Elektrochem. 30, 508, (1924).
(1977). 270. P. Vanysek, TrAC, Trends Anal. Chem. 12, 357, (1993).
232. M. Gros, S. Gromb, C. Gavach, J. Electroanal. Chem. 89, 29, (1978). 271. A. Volkov, D. W. Deamer, eds. Liquid-Liquid Interfaces. Theory and
233. Z. Samec, V. Marecek, D. Homolka, J. Electroanal. Chem. 187, 31, Methods. 1st ed. CRC, Boca Raton, 1996. 448 pp.
(1985). 272. A. G. Volkov, V. S. Markin, Electrochemical double layers: liquid-liquid
234. H. H. Girault, D. J. Schiffrin, J. Electroanal. Chem. 150, 43, (1983). interfaces, in Encyclopedia of Electrochemistry. Wiley-VCH, New York,
235. H. H. Girault, Electrochim. Acta. 32, 383, (1987). 2003, p. 162.
236. H. H. J. Girault, D. J. Schiffrin, J. Electroanal. Chem. 170, 127, (1984). 273. A. G. Volkov, V. S. Markin, Electric properties of oil/water interfaces,
237. C. M. Pereira, W. Schmickler, A. F. Silva, M. J. Sousa, Chem. Phys. Lett. in Emulsions: Structure, stability and interactions, 4, D. Petsev, Editor.
268, 13, (1997). Academic Press, New York, 2004, p. 91.
238. D. J. Henderson, W. Schmickler, J. Chem. Soc., Faraday Trans. 92,
3839, (1996).

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